Chamber conditioning and removal processes

ABSTRACT

Exemplary methods for conditioning a processing region of a semiconductor processing chamber may include forming conditioning plasma effluents of an oxygen-containing precursor in a semiconductor processing chamber. The methods may include contacting interior surfaces of the semiconductor processing chamber bordering a substrate processing region with the conditioning plasma effluents. The methods may also include treating the interior surfaces of the semiconductor processing chamber.

TECHNICAL FIELD

The present technology relates to semiconductor processes and equipment. More specifically, the present technology relates to etching materials subsequent a chamber conditioning process.

BACKGROUND

Integrated circuits are made possible by processes which produce intricately patterned material layers on substrate surfaces. Producing patterned material on a substrate requires controlled methods for removal of exposed material. Chemical etching is used for a variety of purposes including transferring a pattern in photoresist into underlying layers, thinning layers, or thinning lateral dimensions of features already present on the surface. Often it is desirable to have an etch process that etches one material faster than another facilitating, for example, a pattern transfer process. Such an etch process is said to be selective to the first material. As a result of the diversity of materials, circuits, and processes, etch processes have been developed with a selectivity towards a variety of materials.

Etch processes may be termed wet or dry based on the materials used in the process. A wet HF etch preferentially removes silicon oxide over other dielectrics and materials. However, wet processes may have difficulty penetrating some constrained trenches and also may sometimes deform the remaining material. Dry etches produced in local plasmas formed within the substrate processing region can penetrate more constrained trenches and exhibit less deformation of delicate remaining structures. However, local plasmas may damage the substrate through the production of electric arcs as they discharge. Additionally, plasma effluents may impact subsequent processing of additional substrates.

Thus, there is a need for improved systems and methods that can be used to produce high quality devices and structures. These and other needs are addressed by the present technology.

SUMMARY

Exemplary methods for conditioning a processing region of a semiconductor processing chamber may include forming conditioning plasma effluents of an oxygen-containing precursor in a semiconductor processing chamber. The methods may include contacting interior surfaces of the semiconductor processing chamber bordering a substrate processing region with the conditioning plasma effluents. The methods may also include treating the interior surfaces of the semiconductor processing chamber

In some embodiments, the methods may also include transferring a substrate into the substrate processing region subsequent the operation of treating the interior surfaces with the conditioning plasma effluents. The substrate may include an exposed region of titanium nitride. The methods may include flowing a fluorine-containing precursor into a remote plasma region fluidly coupled with the substrate processing region while forming a remote plasma in the remote plasma region to produce etching plasma effluents. The methods may include etching the exposed region of titanium nitride by flowing the etching plasma effluents into the substrate processing region through apertures in a showerhead. The showerhead may be disposed between the remote plasma region and the substrate processing region. The substrate may further include an exposed region of tungsten, and the etching may remove titanium nitride at a selectivity relative to tungsten of greater than or about 100:1. An amount of titanium nitride at an edge region of the substrate and an amount of titanium nitride at a central region of the substrate may be etched to within about 5% of one another.

The methods may also include flowing a hydrogen-containing precursor with the fluorine-containing precursor to produce the etching plasma effluents. The hydrogen-containing precursor may be hydrogen or ammonia. The methods may also include flowing an oxygen-containing precursor with the fluorine-containing precursor to produce the etching plasma effluents. A temperature of the substrate may be maintained between about 200° C. and about 500° C. during the etching. The substrate processing region may be essentially devoid of hydrogen during the operation of treating the interior surfaces of the semiconductor processing chamber with the conditioning plasma effluents. The conditioning plasma effluents may be produced locally in the substrate processing region of the semiconductor processing chamber. The conditioning plasma effluents may also be produced in a remote plasma region and may be flowed from the remote plasma region into the substrate processing region. A plasma power used to produce the conditioning plasma effluents may be less than or about 500 W. The substrate processing region may be defined from above by a showerhead, and a pedestal within the substrate processing region may be maintained within about 5 cm of the showerhead during the treating.

The present technology may also encompass methods including forming conditioning plasma effluents of a fluorine-containing precursor and an oxygen-containing precursor in a semiconductor processing chamber. The methods may include contacting interior surfaces of the semiconductor processing chamber bordering a substrate processing region with the conditioning plasma effluents. The methods may also include treating the interior surfaces of the semiconductor processing chamber.

In some embodiments, the methods may also include transferring a substrate into the substrate processing region subsequent the operation of treating the interior surfaces with the conditioning plasma effluents. The substrate may include an exposed region of titanium nitride. The methods may include flowing a fluorine-containing precursor into a remote plasma region fluidly coupled with the substrate processing region while forming a remote plasma in the remote plasma region to produce etching plasma effluents. The methods may also include etching the exposed region of titanium nitride by flowing the etching plasma effluents into the substrate processing region through apertures in a showerhead. The showerhead may be disposed between the remote plasma region and the substrate processing region. A pressure within the semiconductor processing chamber may be maintained between about 1 Torr and about 10 Torr. A temperature of the substrate may be maintained between about 200° C. and about 500° C.

The present technology may also encompass methods including forming conditioning plasma effluents of a fluorine-containing precursor and an oxygen-containing precursor in a semiconductor processing chamber. The methods may include contacting interior surfaces of the semiconductor processing chamber bordering a substrate processing region with the conditioning plasma effluents. The methods may include treating the interior surfaces of the semiconductor processing chamber. The methods may include transferring a substrate into the substrate processing region, and the substrate may include an exposed region of titanium nitride. The methods may also include flowing a fluorine-containing precursor into the substrate processing region. The methods may also include etching the exposed region of titanium nitride by contacting the exposed region of titanium nitride with the fluorine-containing precursor. A temperature of the substrate may be maintained between about 200° C. and about 500° C. during the etching. An amount of titanium nitride at an edge region of the substrate and an amount of titanium nitride at a central region of the substrate may be etched to within about 5% of one another.

Such technology may provide numerous benefits over conventional systems and techniques. For example, the etching methods may remove titanium nitride selectively relative to numerous other materials. Additionally, the process may provide uniformity of the etch process and stability of the process between substrates. These and other embodiments, along with many of their advantages and features, are described in more detail in conjunction with the below description and attached figures.

BRIEF DESCRIPTION OF THE DRAWINGS

A further understanding of the nature and advantages of the disclosed technology may be realized by reference to the remaining portions of the specification and the drawings.

FIG. 1 shows a top plan view of one embodiment of an exemplary processing system according to embodiments of the present technology.

FIG. 2A shows a schematic cross-sectional view of an exemplary processing chamber according to embodiments of the present technology.

FIG. 2B shows a detailed view of a portion of the processing chamber illustrated in FIG. 2A according to embodiments of the present technology.

FIG. 3 shows a bottom plan view of an exemplary showerhead according to embodiments of the present technology.

FIG. 4 shows exemplary operations in a method according to embodiments of the present technology.

Several of the figures are included as schematics. It is to be understood that the figures are for illustrative purposes, and are not to be considered of scale unless specifically stated to be of scale. Additionally, as schematics, the figures are provided to aid comprehension and may not include all aspects or information compared to realistic representations, and may include exaggerated material for illustrative purposes.

In the appended figures, similar components and/or features may have the same reference label. Further, various components of the same type may be distinguished by following the reference label by a letter that distinguishes among the similar components. If only the first reference label is used in the specification, the description is applicable to any one of the similar components having the same first reference label irrespective of the letter.

DETAILED DESCRIPTION

As semiconductor device features continue to reduce in size, improving selectivity and uniformity of etch processes becomes increasingly important. Etch processes performed to remove a variety of materials may produce byproducts either from etched materials, or from the precursors used as the etchant. Although conventional technologies utilize pumps and other flow characteristics to remove these materials from the semiconductor processing chamber, some materials may adhere to chamber walls and may remain during subsequent substrate processing. For example, etch processes utilizing fluorine-containing precursors may produce multiple reactants including fluorine radical species during plasma processing. Fluorine radicals may adhere to chamber sidewalls or interior surfaces. When a subsequent etch process is performed on the next substrate in a batch, these retained fluorine radicals may impact the etch process, and may affect uniformity of the etch along edge regions of the substrate that may be nearer to the chamber sidewalls.

The present technology overcomes these issues by performing a chamber conditioning process that may be performed before an etch process is begun, and may be performed between each successive etch process. The conditioning or treatment operations may facilitate removal of residual effluents or materials within the chamber. This may increase not only the uniformity of each etch process performed, but may also improve the stability of the process from substrate-to-substrate. By flowing an oxygen-containing precursor during the treatment, residual fluorine radicals or species adhering to chamber sidewalls may be oxidized and removed from the chamber. Uniformity of subsequent etch processes may then be improved, along with more consistent etching between substrates.

Although the remaining disclosure will routinely identify specific etching processes utilizing the disclosed technology, it will be readily understood that the systems and methods are equally applicable to deposition and cleaning processes as may occur in the described chambers. Accordingly, the technology should not be considered to be so limited as for use with etching processes or chambers alone. Moreover, although an exemplary chamber is described to provide foundation for the present technology, it is to be understood that the present technology can be applied to virtually any semiconductor processing chamber that may allow the single-chamber operations described.

FIG. 1 shows a top plan view of one embodiment of a processing system 100 of deposition, etching, baking, and curing chambers according to embodiments. In the figure, a pair of front opening unified pods (FOUPs) 102 supply substrates of a variety of sizes that are received by robotic arms 104 and placed into a low pressure holding area 106 before being placed into one of the substrate processing chambers 108 a-f, positioned in tandem sections 109 a-c. A second robotic arm 110 may be used to transport the substrate wafers from the holding area 106 to the substrate processing chambers 108 a-f and back. Each substrate processing chamber 108 a-f, can be outfitted to perform a number of substrate processing operations including the dry etch processes described herein in addition to cyclical layer deposition (CLD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), etch, pre-clean, degas, orientation, and other substrate processes.

The substrate processing chambers 108 a-f may include one or more system components for depositing, annealing, curing and/or etching a dielectric or metallic film on the substrate wafer. In one configuration, two pairs of the processing chambers, e.g., 108 c-d and 108 e-f, may be used to deposit material on the substrate, and the third pair of processing chambers, e.g., 108 a-b, may be used to etch the deposited material. In another configuration, all three pairs of chambers, e.g., 108 a-f, may be configured to etch a dielectric or metallic film on the substrate. Any one or more of the processes described may be carried out in chamber(s) separated from the fabrication system shown in different embodiments. It will be appreciated that additional configurations of deposition, etching, annealing, and curing chambers for dielectric films are contemplated by system 100.

FIG. 2A shows a cross-sectional view of an exemplary process chamber system 200 with partitioned plasma generation regions within the processing chamber. During film etching, e.g., titanium nitride, tantalum nitride, tungsten, copper, cobalt, silicon, polysilicon, silicon oxide, silicon nitride, silicon oxynitride, silicon oxycarbide, etc., a process gas may be flowed into the first plasma region 215 through a gas inlet assembly 205. A remote plasma system (RPS) 201 may optionally be included in the system, and may process a first gas which then travels through gas inlet assembly 205. The inlet assembly 205 may include two or more distinct gas supply channels where the second channel (not shown) may bypass the RPS 201, if included.

A cooling plate 203, faceplate 217, ion suppressor 223, showerhead 225, and a substrate support 265, having a substrate 255 disposed thereon, are shown and may each be included according to embodiments. The pedestal 265 may have a heat exchange channel through which a heat exchange fluid flows to control the temperature of the substrate, which may be operated to heat and/or cool the substrate or wafer during processing operations. The wafer support platter of the pedestal 265, which may comprise aluminum, ceramic, or a combination thereof, may also be resistively heated in order to achieve relatively high temperatures, such as from up to or about 100° C. to above or about 600° C., using an embedded resistive heater element.

The faceplate 217 may be pyramidal, conical, or of another similar structure with a narrow top portion expanding to a wide bottom portion. The faceplate 217 may additionally be flat as shown and include a plurality of through-channels used to distribute process gases. Plasma generating gases and/or plasma excited species, depending on use of the RPS 201, may pass through a plurality of holes, shown in FIG. 2B, in faceplate 217 for a more uniform delivery into the first plasma region 215.

Exemplary configurations may include having the gas inlet assembly 205 open into a gas supply region 258 partitioned from the first plasma region 215 by faceplate 217 so that the gases/species flow through the holes in the faceplate 217 into the first plasma region 215. Structural and operational features may be selected to prevent significant backflow of plasma from the first plasma region 215 back into the supply region 258, gas inlet assembly 205, and fluid supply system 210. The faceplate 217, or a conductive top portion of the chamber, and showerhead 225 are shown with an insulating ring 220 located between the features, which allows an AC potential to be applied to the faceplate 217 relative to showerhead 225 and/or ion suppressor 223. The insulating ring 220 may be positioned between the faceplate 217 and the showerhead 225 and/or ion suppressor 223 enabling a capacitively coupled plasma (CCP) to be formed in the first plasma region. A baffle (not shown) may additionally be located in the first plasma region 215, or otherwise coupled with gas inlet assembly 205, to affect the flow of fluid into the region through gas inlet assembly 205.

The ion suppressor 223 may comprise a plate or other geometry that defines a plurality of apertures throughout the structure that are configured to suppress the migration of ionically-charged species out of the first plasma region 215 while allowing uncharged neutral or radical species to pass through the ion suppressor 223 into an activated gas delivery region between the suppressor and the showerhead. In embodiments, the ion suppressor 223 may comprise a perforated plate with a variety of aperture configurations. These uncharged species may include highly reactive species that are transported with less reactive carrier gas through the apertures. As noted above, the migration of ionic species through the holes may be reduced, and in some instances completely suppressed. Controlling the amount of ionic species passing through the ion suppressor 223 may advantageously provide increased control over the gas mixture brought into contact with the underlying wafer substrate, which in turn may increase control of the deposition and/or etch characteristics of the gas mixture. For example, adjustments in the ion concentration of the gas mixture can significantly alter its etch selectivity, e.g., SiNx:SiOx etch ratios, Si:SiOx etch ratios, etc. In alternative embodiments in which deposition is performed, it can also shift the balance of conformal-to-flowable style depositions for dielectric materials.

The plurality of apertures in the ion suppressor 223 may be configured to control the passage of the activated gas, i.e., the ionic, radical, and/or neutral species, through the ion suppressor 223. For example, the aspect ratio of the holes, or the hole diameter to length, and/or the geometry of the holes may be controlled so that the flow of ionically-charged species in the activated gas passing through the ion suppressor 223 is reduced. The holes in the ion suppressor 223 may include a tapered portion that faces the plasma excitation region 215, and a cylindrical portion that faces the showerhead 225. The cylindrical portion may be shaped and dimensioned to control the flow of ionic species passing to the showerhead 225. An adjustable electrical bias may also be applied to the ion suppressor 223 as an additional means to control the flow of ionic species through the suppressor.

The ion suppressor 223 may function to reduce or eliminate the amount of ionically charged species traveling from the plasma generation region to the substrate. Uncharged neutral and radical species may still pass through the openings in the ion suppressor to react with the substrate. It should be noted that the complete elimination of ionically charged species in the reaction region surrounding the substrate may not be performed in embodiments. In certain instances, ionic species are intended to reach the substrate in order to perform the etch and/or deposition process. In these instances, the ion suppressor may help to control the concentration of ionic species in the reaction region at a level that assists the process.

Showerhead 225 in combination with ion suppressor 223 may allow a plasma present in first plasma region 215 to avoid directly exciting gases in substrate processing region 233, while still allowing excited species to travel from chamber plasma region 215 into substrate processing region 233. In this way, the chamber may be configured to prevent the plasma from contacting a substrate 255 being etched. This may advantageously protect a variety of intricate structures and films patterned on the substrate, which may be damaged, dislocated, or otherwise warped if directly contacted by a generated plasma. Additionally, when plasma is allowed to contact the substrate or approach the substrate level, the rate at which oxide species etch may increase. Accordingly, if an exposed region of material is oxide, this material may be further protected by maintaining the plasma remotely from the substrate.

The processing system may further include a power supply 240 electrically coupled with the processing chamber to provide electric power to the faceplate 217, ion suppressor 223, showerhead 225, and/or pedestal 265 to generate a plasma in the first plasma region 215 or processing region 233. The power supply may be configured to deliver an adjustable amount of power to the chamber depending on the process performed. Such a configuration may allow for a tunable plasma to be used in the processes being performed. Unlike a remote plasma unit, which is often presented with on or off functionality, a tunable plasma may be configured to deliver a specific amount of power to the plasma region 215. This in turn may allow development of particular plasma characteristics such that precursors may be dissociated in specific ways to enhance the etching profiles produced by these precursors.

A plasma may be ignited either in chamber plasma region 215 above showerhead 225 or substrate processing region 233 below showerhead 225. Plasma may be present in chamber plasma region 215 to produce the radical precursors from an inflow of, for example, a fluorine-containing precursor or other precursor. An AC voltage typically in the radio frequency (RF) range may be applied between the conductive top portion of the processing chamber, such as faceplate 217, and showerhead 225 and/or ion suppressor 223 to ignite a plasma in chamber plasma region 215 during deposition. An RF power supply may generate a high RF frequency of 13.56 MHz but may also generate other frequencies alone or in combination with the 13.56 MHz frequency.

FIG. 2B shows a detailed view 253 of the features affecting the processing gas distribution through faceplate 217. As shown in FIGS. 2A and 2B, faceplate 217, cooling plate 203, and gas inlet assembly 205 intersect to define a gas supply region 258 into which process gases may be delivered from gas inlet 205. The gases may fill the gas supply region 258 and flow to first plasma region 215 through apertures 259 in faceplate 217. The apertures 259 may be configured to direct flow in a substantially unidirectional manner such that process gases may flow into processing region 233, but may be partially or fully prevented from backflow into the gas supply region 258 after traversing the faceplate 217.

The gas distribution assemblies such as showerhead 225 for use in the processing chamber section 200 may be referred to as dual channel showerheads (DCSH) and are additionally detailed in the embodiments described in FIG. 3. The dual channel showerhead may provide for etching processes that allow for separation of etchants outside of the processing region 233 to provide limited interaction with chamber components and each other prior to being delivered into the processing region.

The showerhead 225 may comprise an upper plate 214 and a lower plate 216. The plates may be coupled with one another to define a volume 218 between the plates. The coupling of the plates may be so as to provide first fluid channels 219 through the upper and lower plates, and second fluid channels 221 through the lower plate 216. The formed channels may be configured to provide fluid access from the volume 218 through the lower plate 216 via second fluid channels 221 alone, and the first fluid channels 219 may be fluidly isolated from the volume 218 between the plates and the second fluid channels 221. The volume 218 may be fluidly accessible through a side of the gas distribution assembly 225.

FIG. 3 is a bottom view of a showerhead 325 for use with a processing chamber according to embodiments. Showerhead 325 may correspond with the showerhead 225 shown in FIG. 2A. Through-holes 365, which show a view of first fluid channels 219, may have a plurality of shapes and configurations in order to control and affect the flow of precursors through the showerhead 225. Small holes 375, which show a view of second fluid channels 221, may be distributed substantially evenly over the surface of the showerhead, even amongst the through-holes 365, and may help to provide more even mixing of the precursors as they exit the showerhead than other configurations.

The chambers discussed previously may be used in performing exemplary methods including etching methods. Turning to FIG. 4, exemplary operations of a method 400 according to embodiments of the present technology are shown. During some or all of the operations of method 400, no substrate or some sort of dummy or unprocessed substrate may be present in the substrate processing region of a semiconductor processing chamber. The method may include flowing one or more precursors into a remote plasma region at optional operation 405. In some embodiments, the precursors may be flowed directly into a substrate processing region where a plasma may be ignited locally. In either scenario, the method may include striking a plasma to produce plasma effluents, which may be conditioning plasma effluents at operation 410. When formed in a remote plasma region, the conditioning plasma effluents may be flowed into the processing region of the chamber at operation 415. Sidewalls, a pedestal, a showerhead, or other chamber components noted previously may be contacted by the conditioning plasma effluents on interior surfaces that may define the substrate processing region of the semiconductor processing chamber. The methods may then treat the interior chamber surfaces of the semiconductor processing chamber at operation 420.

Method 400 may include additional optional operations in which a substrate may be processed subsequent the treatment. For example, at optional operation 425, a substrate may be delivered or transferred to the substrate processing region of the semiconductor processing chamber. The substrate may have been processed prior to the transfer, and the processing may include feature formation, which may include deposition, etching, or other fabrication processes. In an exemplary process, the substrate may be characterized by one or more exposed materials on the substrate. For example, the substrate may include exposed regions of titanium nitride, tungsten, silicon oxide, silicon nitride, or other silicon-containing, nitrogen-containing, oxygen-containing, carbon-containing, or metal containing materials. Method 400 may also include selectively etching one or more of the materials, such as titanium nitride, at optional operation 430.

The etching operation may be performed in one or more ways, and in embodiments the etching may be performed by a plasma-enhanced dry etch process. As will be discussed further below, treating the chamber as discussed may facilitate uniformity improvements of the etching when the etchant precursors include a fluorine-containing precursor. For example, the etching process may include flowing a fluorine-containing precursor into a remote plasma region fluidly coupled with the substrate processing region in which the substrate has been positioned. The remote plasma region may be separated from the substrate processing region with one or more components, such as a showerhead and/or an ion suppressor as described previously. Etching plasma effluents may be produced from the fluorine-containing precursor and delivered to the substrate processing region through apertures or through-holes of the ion suppressor and/or the showerhead. The exposed region of titanium nitride may be etched with the etching plasma effluents selective to other exposed materials on the substrate.

In some embodiments the etching may be performed without plasma enhancement. For example, one or more fluorine-containing precursors may be flowed directly into the substrate processing region. The fluorine-containing precursors may interact with the exposed region of titanium nitride, and may etch the titanium nitride selective to other exposed materials. By performing a selective etch of titanium nitride, maintaining other materials within a device structure may be improved to minimize or prevent loss. For example, in some DRAM structures, tungsten may be seated in trenches formed in silicon-containing materials, such as silicon oxide, silicon nitride, or silicon, and one or more liner materials may be disposed about the trench, such as titanium or tantalum nitride. Processing may include removing the exposed nitride liner while maintaining the tungsten.

Conventional processing, including plasma processing may at least partially etch the tungsten as well through one or more mechanisms. For example, local plasma formation may expose the tungsten to ionic species produced, which may perform a bombardment effect on the tungsten, lowering the selectivity relative to nitride. By producing etching plasma precursors remotely in some embodiments of the present technology, the ions may be filtered from the plasma effluents by the ion suppressor, which may improve the etch selectivity to nitride relative to tungsten, silicon oxide, or silicon nitride. Because of the benefits that may additionally be provided by the chamber, a number of precursors may be utilized in the present technology. The remote plasma region may be located within a distinct module separate from the processing chamber, such as an RPS unit, or within a partitioned region within the processing chamber. The separate plasma region may be fluidly coupled with the substrate processing region by apertures in a showerhead and/or ion suppressor positioned between the two regions.

In either plasma or non-plasma processing, nitrogen trifluoride may be used as the fluorine-containing precursor utilized in the etching. Other sources of fluorine may be used to augment or replace the nitrogen trifluoride. In general, an etching fluorine-containing precursor may be flowed into the remote plasma region or delivered directly to the substrate processing region, and the etching fluorine-containing precursor may include one or more of atomic fluorine, diatomic fluorine, boron trifluoride, chlorine trifluoride, nitrogen trifluoride, hydrogen fluoride, perfluorinated hydrocarbons, sulfur hexafluoride, chlorine trifluoride, and xenon hexafluoride. Nitrogen trifluoride may offer a benefit during plasma processes as the precursor may form long-lived radical fluorine in the conditioning plasma effluents and the etching plasma effluents. Radical fluorine formed from nitrogen trifluoride remains highly reactive even after passing through showerheads and/or ion suppression elements described herein.

One or more hydrogen-containing precursors may also be included in the etching precursors, and may be included in plasma and non-plasma embodiments. For example, diatomic hydrogen, ammonia, or other hydrogen-containing materials may be included with the fluorine-containing precursor to facilitate the etching. Additionally, oxygen or an oxygen-containing precursor may be flowed with the fluorine-containing precursor to produce etchant species.

In each remote plasma or local plasma described herein, the flows of the precursors into the remote plasma region may further include one or more relatively inert gases or carrier gases such as He, N₂, or Ar. The inert gas can be used to improve plasma stability, ease plasma initiation, and improve process uniformity. Argon may promote the formation of a stable plasma. Process uniformity may be generally increased when helium is included. These additives may be included with various embodiments of the present technology. Flow rates and ratios of the different gases may be used to control etch rates and etch selectivity.

As previously discussed, the conditioning plasma may be formed from an oxygen-containing precursor, such as oxygen, ozone, nitrogen-and-oxygen-containing precursors, or other oxygen-containing materials. When fluorine-containing precursors are used in etching operations including plasma processing, one or more etchant species may be developed including hydrogen fluoride, and various fluorine and nitrogen-and-fluorine radical materials including radical fluorine. Without intending to limit the present disclosure to any particular theory, radical fluorine may have one or more competing or limiting effects on etch rates and selectivity of etching operations relative to other etchant species, such as hydrogen fluoride species, for example. Additionally, radical fluorine may not as readily be withdrawn from a processing chamber subsequent etching operations, and may adhere to interior surfaces of the processing chamber. On subsequent etching operations, such as in subsequent cycles or with subsequently processed substrates, residual fluorine adhering to the interior surfaces of the processing chamber may impact the etching being performed. Because the fluorine will be localized near edge regions of the substrate, the etching may be reduced along edge regions, and may produce reduced uniformity between central regions of the substrate and edge regions nearer to the chamber sidewalls.

However, when a treatment is performed such as described in relation to method 400, the residual fluorine may be removed from the chamber, improving etch uniformity as well as consistency of processing substrate-to-substrate. The treatment operations may include an oxygen-containing precursor as previously discussed in order to oxidize the radical fluorine and desorb the fluorine from the chamber surfaces. By performing the treatments according to embodiments of the present technology, etch uniformity may be improved. For example, an amount of titanium nitride at an edge region of the substrate and an amount of titanium nitride at a central region of the substrate may be etched to within less than or about 10% of one another when treatments are performed according to the present technology. In some embodiments, an amount of titanium nitride at an edge region of the substrate and an amount of titanium nitride at a central region of the substrate may be etched to within less than or about 8% of each other, less than or about 6%, less than or about 5%, less than or about 4%, less than or about 3%, less than or about 2%, less than or about 1%, or may be etched substantially or essentially equally when a treatment is performed according to the present technology.

The plasma used during the conditioning operation may be generated using known techniques including radio frequency excitations, capacitively-coupled power, inductively coupled power, or other formation techniques. In some embodiments, the energy may be applied using a capacitively-coupled plasma formed within the processing chamber as previously described. The remote plasma source power may be between about 100 watts and about 3000 watts, and may be between about 200 watts and about 1000 watts, or between about 250 watts and about 500 watts in embodiments. The chamber treatment may also involve a local plasma excitation instead of or in addition to the remote plasma excitation according to some embodiments. The plasma powers of local plasmas used to perform treatment operations may involve application of the same plasma powers as the remote plasmas in embodiments. By maintaining relatively low plasma power during the conditioning operations, less damage may be caused to chamber components, and more controlled dissociation of precursors may be performed.

The conditioning or treatment operations may include one or more additional precursors with the oxygen-containing precursor. For example, carrier gases or inert precursors as described previously may be included in the precursors used. Additionally, a fluorine-containing precursor, such as any of the previously-noted precursors, may be included in the treatment operations. By including a fluorine-containing precursor, such as nitrogen trifluoride, for example, the effect of the treatment operation on the chamber may be tempered. When oxygen-containing precursors are used alone, the effect on the chamber components may be more pronounced, and may limit the predictability of subsequent etching operations. However, when a flow of nitrogen trifluoride or another fluorine-containing precursor is included, a controlled treatment or conditioning process may be performed that allows consistent etching substrate-to-substrate, and which may facilitate predictability of etch rates, etch amounts, and selectivity. Although additional precursors may also be included, in some embodiments the conditioning plasma effluents may be essentially devoid of hydrogen. When hydrogen-containing precursors, such as ammonia, for example, are included in the conditioning operations, residual hydrogen-containing species may be maintained in the chamber, which may affect the selectivity of subsequently performed etching operations.

Chamber components may also be specifically located within the processing chamber during the treatment operations. For example, in some embodiments a pedestal may be raised to a position proximate a showerhead. By raising the pedestal, conditioning plasma effluents flowing through a showerhead may be directed more turbulently through the chamber increasing the contact with chamber sidewalls in lower portions of the processing chamber within the substrate processing region. The raised pedestal may create a more dramatic flow profile of the conditioning plasma effluents, which may improve the conditioning operations. Accordingly, in some embodiments, during the treatment or conditioning operations, a top surface of a puck or pedestal within the substrate processing region may be maintained less than or about 10 cm from the surface of the showerhead or structure defining the substrate processing region from above. In some embodiments the surface of the pedestal may be maintained less than or about 8 cm from the surface of the showerhead, less than or about 6 cm from the surface of the showerhead, less than or about 5 cm from the surface of the showerhead, less than or about 4 cm from the surface of the showerhead, less than or about 3 cm from the surface of the showerhead, less than or about 2 cm from the surface of the showerhead, less than or about 1 cm from the surface of the showerhead, less than or about 0.5 cm from the surface of the showerhead, or less.

By performing processes according to the present technology, titanium nitride may be selectively etched relative to other exposed materials on the substrate. The etch selectivity, which may be defined as the rate of removal of titanium nitride relative to tungsten, silicon oxide, silicon nitride, or other materials, may be greater than or about 50:1, and may be greater than or about 100:1, greater than or about 150:1, greater than or about 200:1, greater than or about 250:1, greater than or about 300:1, greater than or about 500:1, greater than or about 1000:1, greater than or about 2000:1, greater than or about 3000:1, or more. Subsequent the etching operation, which may be performed in one or more cycles, the substrate may be removed from the processing chamber. An additional treatment process may then be performed prior to etching an additional substrate.

The conditioning operations may be performed for time periods of less than or about 5 minutes in embodiments, and may be performed for time periods of less than or about 4 minutes, less than or about 3 minutes, less than or about 2 minutes, less than or about 1 minute, or less. Other process conditions may impact the performance of the operations as well. For example, a pressure within the chamber may be maintained below or about 20 Torr in embodiments. The pressure may be maintained below or about 15 Torr in embodiments, and may be maintained below or about 10 Torr, below or about 5 Torr, below or about 4 Torr, below or about 3 Torr, or below or about 2 Torr. The pressure may also be maintained above or about 1 Torr, above or about 3 Torr, or between about 1 Torr and about 7 Torr. When pressures are reduced below about 1 Torr, the etch rates may slow or etching may cease completely. Additionally, when pressures increase above or about 7 Torr, etching may increase in different materials reducing selectivity to the titanium nitride.

The temperature of the etching and or conditioning operations may be maintained above or about 100° C. in embodiments, and may be maintained above or about 150° C., above or about 200° C., above or about 250° C., above or about 300° C., above or about 350° C., above or about 400° C., above or about 450° C., above or about 500° C., or higher, as well as within any ranges defined within these ranges. Fluorides produced from the titanium nitride may be characterized by lower volatility at temperatures below or about 100° C. or more, and thus higher temperatures may facilitate removal. Additionally, when temperatures are maintained above or about 300° C., plasma enhancement may not be used during the etching operations. By performing etch processes with chamber conditioning according to embodiments of the present technology, increased uniformity of processing as well as improved stability substrate-to-substrate may be afforded.

In the preceding description, for the purposes of explanation, numerous details have been set forth in order to provide an understanding of various embodiments of the present technology. It will be apparent to one skilled in the art, however, that certain embodiments may be practiced without some of these details, or with additional details.

Having disclosed several embodiments, it will be recognized by those of skill in the art that various modifications, alternative constructions, and equivalents may be used without departing from the spirit of the embodiments. Additionally, a number of well-known processes and elements have not been described in order to avoid unnecessarily obscuring the present technology. Accordingly, the above description should not be taken as limiting the scope of the technology. Additionally, methods or processes may be described as sequential or in steps, but it is to be understood that the operations may be performed concurrently, or in different orders than listed.

Where a range of values is provided, it is understood that each intervening value, to the smallest fraction of the unit of the lower limit, unless the context clearly dictates otherwise, between the upper and lower limits of that range is also specifically disclosed. Any narrower range between any stated values or unstated intervening values in a stated range and any other stated or intervening value in that stated range is encompassed. The upper and lower limits of those smaller ranges may independently be included or excluded in the range, and each range where either, neither, or both limits are included in the smaller ranges is also encompassed within the technology, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included.

As used herein and in the appended claims, the singular forms “a”, “an”, and “the” include plural references unless the context clearly dictates otherwise. Thus, for example, reference to “a precursor” includes a plurality of such precursors, and reference to “the layer” includes reference to one or more layers and equivalents thereof known to those skilled in the art, and so forth.

Also, the words “comprise(s)”, “comprising”, “contain(s)”, “containing”, “include(s)”, and “including”, when used in this specification and in the following claims, are intended to specify the presence of stated features, integers, components, or operations, but they do not preclude the presence or addition of one or more other features, integers, components, operations, acts, or groups. 

The invention claimed is:
 1. A method comprising: forming conditioning plasma effluents of an oxygen-containing precursor in a semiconductor processing chamber, wherein the conditioning plasma effluents are produced locally in a substrate processing region of the semiconductor processing chamber; contacting interior surfaces of the semiconductor processing chamber bordering the substrate processing region with the conditioning plasma effluents; and treating the interior surfaces of the semiconductor processing chamber, wherein the treating includes oxidizing fluorine radicals and removing residual fluorine from the interior surfaces of the semiconductor processing chamber, wherein the substrate processing region is essentially devoid of hydrogen during the operation of treating the interior surfaces of the semiconductor processing chamber with the conditioning plasma effluents.
 2. The method of claim 1, further comprising: transferring a substrate into the substrate processing region subsequent the operation of treating the interior surfaces with the conditioning plasma effluents, wherein the substrate comprises an exposed region of titanium nitride; flowing a fluorine-containing precursor into a remote plasma region fluidly coupled with the substrate processing region while forming a remote plasma in the remote plasma region to produce etching plasma effluents; and etching the exposed region of titanium nitride by flowing the etching plasma effluents into the substrate processing region through apertures in a showerhead, wherein the showerhead is disposed between the remote plasma region and the substrate processing region.
 3. The method of claim 2, wherein the substrate further includes an exposed region of tungsten, and wherein the etching removes titanium nitride at a selectivity relative to tungsten of greater than or about 100:1.
 4. The method of claim 2, wherein an amount of titanium nitride at an edge region of the substrate and an amount of titanium nitride at a central region of the substrate are etched to within about 5% of one another.
 5. The method of claim 2, further comprising flowing a hydrogen-containing precursor with the fluorine-containing precursor to produce the etching plasma effluents.
 6. The method of claim 5, wherein the hydrogen-containing precursor is hydrogen or ammonia.
 7. The method of claim 2, further comprising flowing an oxygen-containing precursor with the fluorine-containing precursor to produce the etching plasma effluents.
 8. The method of claim 2, wherein a temperature of the substrate is maintained between about 200° C. and about 500° C. during the etching.
 9. The method of claim 1, wherein a plasma power used to produce the conditioning plasma effluents is less than or about 500 W.
 10. The method of claim 1, wherein the substrate processing region is defined from above by a showerhead, and wherein a pedestal within the substrate processing region is maintained within about 5 cm of the showerhead during the treating.
 11. A method comprising: forming conditioning plasma effluents of a fluorine-containing precursor and an oxygen-containing precursor in a substrate processing region of a semiconductor processing chamber; contacting interior surfaces of the semiconductor processing chamber bordering the substrate processing region with the conditioning plasma effluents; and treating the interior surfaces of the semiconductor processing chamber, wherein the treating includes oxidizing fluorine radicals and removing residual fluorine from the interior surfaces of the semiconductor processing chamber, wherein the substrate processing region is essentially devoid of hydrogen during the operation of treating the interior surfaces of the semiconductor processing chamber with the conditioning plasma effluents.
 12. The method of claim 11, further comprising: transferring a substrate into the substrate processing region subsequent the operation of treating the interior surfaces with the conditioning plasma effluents, wherein the substrate comprises an exposed region of titanium nitride; flowing a fluorine-containing precursor into a remote plasma region fluidly coupled with the substrate processing region while forming a remote plasma in the remote plasma region to produce etching plasma effluents; and etching the exposed region of titanium nitride by flowing the etching plasma effluents into the substrate processing region through apertures in a showerhead, wherein the showerhead is disposed between the remote plasma region and the substrate processing region.
 13. The method of claim 12, wherein a pressure within the semiconductor processing chamber is maintained between about 1 Torr and about 10 Torr.
 14. The method of claim 12, wherein a temperature of the substrate is maintained between about 200° C. and about 500° C.
 15. A method comprising: forming conditioning plasma effluents of a fluorine-containing precursor and an oxygen-containing precursor in a substrate processing region of a semiconductor processing chamber; contacting interior surfaces of the semiconductor processing chamber bordering the substrate processing region with the conditioning plasma effluents; treating the interior surfaces of the semiconductor processing chamber, wherein the treating includes oxidizing fluorine radicals and removing residual fluorine from the interior surfaces of the semiconductor processing chamber, wherein the substrate processing region is essentially devoid of hydrogen during the operation of treating the interior surfaces of the semiconductor processing chamber with the conditioning plasma effluents; transferring a substrate into the substrate processing region, wherein the substrate comprises an exposed region of titanium nitride; flowing a fluorine-containing precursor into the substrate processing region; and etching the exposed region of titanium nitride by contacting the exposed region of titanium nitride with the fluorine-containing precursor.
 16. The method of claim 15, wherein a temperature of the substrate is maintained between about 200° C. and about 500° C. during the etching.
 17. The method of claim 15, wherein an amount of titanium nitride at an edge region of the substrate and an amount of titanium nitride at a central region of the substrate are etched to within about 5% of one another. 